CN109276764A - A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof - Google Patents
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof Download PDFInfo
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- CN109276764A CN109276764A CN201811234084.XA CN201811234084A CN109276764A CN 109276764 A CN109276764 A CN 109276764A CN 201811234084 A CN201811234084 A CN 201811234084A CN 109276764 A CN109276764 A CN 109276764A
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention discloses a kind of novel calcium and magnesium silicates and fibroin albumen complex stephanoporate bracket, belong to bone defect healing medical material preparation technical field, solves the problems, such as current fibroin material osteoinductive and at vascular performance deficiency, bracket is made of two kinds of materials of calcium and magnesium silicate and fibroin albumen, from the angle of natural bionic, there is the inorganic and organic composite biological material of porous structure using Freeze Drying Technique building, and then promote osteanagenesis, process is simple, it is short the time required to preparation, required low in raw material price, production cost is low, simulate the Nomenclature Composition and Structure of Complexes of internal human body bone, pass through the compound of calcium and magnesium silicate and fibroin albumen, so that the mechanical strength of complex stephanoporate bracket has better access to the mechanical strength of human body cancellous bone, it is formed and the good compatible hydroxyapatite layer of bone, form effective Integrated implant, it and is Bone Defect Repari Region provides mechanical support, and then promotes Bone Defect Repari.
Description
Technical field
The present invention relates to a kind of calcic magnesium silicates for having porous structure and fibroin protein composite bracket and its preparation side
Method, especially bone defect healing medical material preparation technical field disclose a kind of novel bone repairing support and its preparation side
Method.
Background technique
Bone defect healing needs timbering material to have good biocompatibility, and suitable degradation rate is suitble to bone and blood
The pore structure that pipe range enters matches the performances such as the mechanical strength of defect area.Current bone tissue engineering scaffold concentrates on bionical
The Nomenclature Composition and Structure of Complexes of bone.Fibroin albumen is to be widely used in a kind of clinical native protein material, and biology and histocompatbility are good,
Satisfactory mechanical property, degradation property is adjustable, and from a wealth of sources, and preparation is simple, can be by with hydroxyapatite, tricalcium phosphate etc.
It is compound come analog bone composition, but osteoinductive and at vascular performance deficiency, limit its application in bone defect healing.
The silicate biological active ceramic material of calcium-magnesium-containing has good biocompatibility and bioactivity.Its mainly at
Be divided into magnesium, calcium and silicon, stem cell Osteoblast Differentiation and vascular endothelial cell can be promoted at vascularization, and implant site can be with
Body fluid reacts, and is formed and bone and soft tissue all have the hydroxyapatite layer of good biocompatibility, promotes new bone and new
Vascularization.
From the angle of natural bionic, with good skeletonization and the inorganic matter of angiogenesis and there will be good biological compatible
Property organic matter it is compound, be prepared into inorganic with organic composite biological material, be conducive to osteanagenesis.At present with calcium silicon magnesium Ceramic Composite
Organic matter be mainly degradable high polymer (such as polylactic acid) and natural biologic material (such as sodium alginate).But mesh
Before have not yet to see report using the compound fibroin albumen of calcium and magnesium silicate biological active ceramic material.
Fibroin albumen and calcium and magnesium silicate bioactive ceramics is compound, not only can forming with analog bone, can also send out
The bioactivity of calcium and magnesium silicate ceramic ceramic material and the histocompatbility of fibroin albumen are waved, and then promotes osteanagenesis reparation.
Summary of the invention
For shortcoming and defect of the existing technology, the present invention proposes a kind of novel calcium and magnesium silicate and fibroin albumen
Complex stephanoporate bracket and preparation method thereof.From the angle of natural bionic, there is porous structure using Freeze Drying Technique building
Inorganic and organic composite biological material, and then promote osteanagenesis.
To achieve the above object, the invention provides the following technical scheme:
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket, bracket is by calcium and magnesium silicate and two kinds of fibroin albumen
The mass ratio of material composition, calcium and magnesium silicate and fibroin albumen is 1~50:100.
As further scheme of the invention: the partial size of the calcium and magnesium silicate is 0.1~5 μm.
As further scheme of the invention: the calcium and magnesium silicate is akermanite, becomes wollastonite, magnesium doping silicic acid
One or both of calcium, merwinite and monticellite and two or more compounds.
As further scheme of the invention: bracket is porous structure, and porosity is 90%~96%.
Based on the preparation method of the novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket, specific steps are as follows:
(1) calcium and magnesium silicate powder is added in n-butanol by the mass volume ratio of 0.25~20g:100mL, with 200rpm's
Speed is placed in mechanical ball mill 2h in ball grinder；
(2) slurry of ball milling is then subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz；After ultrasonic 10min,
It is 8%~20% that the ratio of above-mentioned dispersion liquid 4:2 by volume, which is added dropwise to mass fraction, under the mixing speed of 200rpm
In silk fibroin protein solution, the mass ratio for controlling calcium and magnesium silicate and fibroin albumen is 1~50:100；
(3) suspension mixed is placed in in -20~-5 °C of refrigerator freezing 10~for 24 hours, then defrosting 6h is obtained at room temperature
To the silk fibroin bracket of white, bracket is cleaned using deionized water, bracket is freeze-dried after cleaning n-butanol, is obtained compound
Porous bone tissue engineering bracket.
The novel calcium and magnesium silicate and purposes of the fibroin albumen complex stephanoporate bracket in bone defect healing.
Compared with prior art, the beneficial effects of the present invention are:
(1) process is simple, and short the time required to preparation, required low in raw material price, production cost is low, calcium and magnesium silicate and fibroin egg
White complex stephanoporate bracket simulates the Nomenclature Composition and Structure of Complexes of internal human body bone；
(2) using n-butanol crosslinking and freeze-drying, the bracket of preparation has the pore structure of three-dimensional communication, and porosity exists
90% or more, aperture is between 50~350 μm；
(3) by the compound of calcium and magnesium silicate and fibroin albumen, so that the mechanical strength of complex stephanoporate bracket has better access to people
The mechanical strength of body cancellous bone；
(4) the calcium and magnesium silicate biological active ceramic material in Bone Defect Repari layer have bioactivity it is high, can be good with bone tissue
In implant site a series of mineralising reactions can occur for the characteristics of bonding, ultimately form and the good compatible hydroxyapatite of bone
Layer forms effective Integrated implant, and provides mechanical support for Bone Defect Repari region, and then promote Bone Defect Repari.
(5) by the connected porous structure of freeze-drying building, the transport of blood vessel grown into nutrition can be promoted, furthermore
Calcium and magnesium silicate can also promote vascular endothelial cell to form blood vessel, and then further promote Bone Defect Repari.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of complex stephanoporate bracket in embodiment 1.
Fig. 2 is the stereoscan photograph of complex stephanoporate bracket in embodiment 1.
Fig. 3 is the stereoscan photograph of the part of complex stephanoporate bracket in embodiment 1.
Specific embodiment
Technical solution of the present invention is described in more detail With reference to embodiment.
Embodiment 1
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof are provided.By akermanite powder
It is added in n-butanol by the mass volume ratio of 2g:100mL, mechanical ball mill 2h in ball grinder is placed in the speed of 200rpm；With
The slurry of ball milling is subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz afterwards；After ultrasonic 10min, in stirring for 200rpm
It mixes and the ratio of above-mentioned dispersion liquid 4:2 by volume is added dropwise in the silk fibroin protein solution that mass fraction is 10% under speed,
The mass ratio for controlling akermanite and fibroin albumen is 10:100；The suspension mixed is placed in -20 °C of refrigerator and is freezed
10h, then defrosting 6h obtains the silk fibroin bracket of white at room temperature, cleans bracket using deionized water, cleans n-butanol
Bracket is freeze-dried afterwards, obtains compound porous bone tissue engineering scaffold.
Using the diffracting spectrum of compound porous bone tissue engineering scaffold prepared by this method as shown in Figure 1, having magnesium yellow
The characteristic diffraction peak of feldspar and fibroin albumen, between the two without generating new object phase.Compound porous bone tissue engineering scaffold
For microscopic appearance figure as shown in Fig. 2, the aperture of bracket is at 100 μm or so, the connectivity in hole is good.This is tested through volume drainage
The porosity of bracket is 91.43%~93.82%, and measuring compression modulus using mechanics machine is 2.72~4.63MPa.Such as Fig. 3
Shown, it is compound porous with fibroin albumen that In vitro cell experiment shows that mesenchymal stem cell enough adheres well to akermanite
On bracket.
Embodiment 2
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof are provided.Wollastonite powder will be become
It is added in n-butanol by the mass volume ratio of 12g:100mL, mechanical ball mill 2h in ball grinder is placed in the speed of 200rpm；With
The slurry of ball milling is subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz afterwards；After ultrasonic 10min, in stirring for 200rpm
It mixes and the ratio of above-mentioned dispersion liquid 4:2 by volume is added dropwise in the silk fibroin protein solution that mass fraction is 15% under speed,
Control becomes the mass ratio of wollastonite and fibroin albumen as 40:100；The suspension mixed is placed in -15 °C of refrigerator and is freezed
12h, then defrosting 6h obtains the silk fibroin bracket of white at room temperature, cleans bracket using deionized water, cleans n-butanol
Bracket is freeze-dried afterwards, obtaining porosity is 83.95%~87.86%, aperture 50 μm or so and compression modulus 4.27~
The compound porous bone tissue engineering scaffold of 6.75MPa.
Embodiment 3
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof are provided.Magnesium is adulterated into calcium silicates
Powder is added in n-butanol by the mass volume ratio of 20g:100mL, is placed in mechanical ball mill in ball grinder with the speed of 200rpm
2h；The slurry of ball milling is then subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz；After ultrasonic 10min,
The ratio of above-mentioned dispersion liquid 4:2 by volume is added dropwise to the fibroin that mass fraction is 20% under the mixing speed of 200rpm
In protein solution, the mass ratio of control magnesium doping calcium silicates and fibroin albumen is 50:100；The suspension mixed is placed in-
16h is freezed in 10 °C of refrigerator, then defrosting 6h obtains the silk fibroin bracket of white at room temperature, cleans using deionized water
Bracket is freeze-dried by bracket after cleaning n-butanol, and obtaining porosity is 79.17%~81.69%, and aperture is at 50 μm or so and presses
Compound porous bone tissue engineering scaffold of the contracting modulus in 6.82~9.47MPa.
Embodiment 4
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof are provided.By merwinite powder
It is added in n-butanol by the mass volume ratio of 1g:100mL, mechanical ball mill 2h in ball grinder is placed in the speed of 200rpm；With
The slurry of ball milling is subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz afterwards；After ultrasonic 10min, in stirring for 200rpm
It mixes and the ratio of above-mentioned dispersion liquid 4:2 by volume is added dropwise in the silk fibroin protein solution that mass fraction is 8% under speed,
The mass ratio for controlling merwinite and fibroin albumen is 6.25:100；The suspension mixed is placed in -5 °C of refrigerator and is freezed
16h, then defrosting 6h obtains the silk fibroin bracket of white at room temperature, cleans bracket using deionized water, cleans n-butanol
Bracket is freeze-dried afterwards, obtaining porosity is 95.04%~97.38%, aperture 350 μm or so and compression modulus 1.68~
The compound porous bone tissue engineering scaffold of 3.25MPa.
Embodiment 5
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof are provided.By monticellite powder
Body is added in n-butanol by the mass volume ratio of 0.25g:100mL, is placed in mechanical ball mill in ball grinder with the speed of 200rpm
2h；The slurry of ball milling is then subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz；After ultrasonic 10min,
The ratio of above-mentioned dispersion liquid 4:2 by volume is added dropwise to the silk that mass fraction is 12.5% under the mixing speed of 200rpm
In fibroin solution, the mass ratio for controlling monticellite and fibroin albumen is 1:100；The suspension mixed is placed in -10 °
It is freezed in the refrigerator of C for 24 hours, then defrosting 6h obtains the silk fibroin bracket of white at room temperature, cleans branch using deionized water
Bracket is freeze-dried by frame after cleaning n-butanol, and obtaining porosity is 92.56%~94.29%, and aperture is at 150 μm or so and presses
Compound porous bone tissue engineering scaffold of the contracting modulus in 2.89~4.72MPa.
Embodiment 6
A kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket and preparation method thereof are provided.By akermanite and
Diopside is mixed in the ratio of 1:1, then is added in n-butanol by the mass volume ratio of 9g:100mL, is set with the speed of 200rpm
The mechanical ball mill 2h in ball grinder；The slurry of ball milling is then subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz；
After ultrasonic 10min, the ratio of above-mentioned dispersion liquid 4:2 by volume is added dropwise to quality point under the mixing speed of 200rpm
Number is 25:100 for the mass ratio in 18% silk fibroin protein solution, controlling monticellite and fibroin albumen；It is outstanding by what is mixed
Supernatant liquid, which is placed in -5 °C of refrigerator, to be freezed for 24 hours, then at room temperature defrosting 6h obtain white silk fibroin bracket, using go from
Sub- water cleans bracket, is freeze-dried bracket after cleaning n-butanol, and obtaining porosity is 84.56%~87.29%, and aperture is in 100 μ
The compound porous bone tissue engineering scaffold of m or so and compression modulus in 5.26~7.74MPa.
Better embodiment of the invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be without departing from the purpose of the present invention
It makes a variety of changes.
Claims (8)
1. a kind of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket, which is characterized in that bracket is by calcium and magnesium silicate
It is formed with two kinds of materials of fibroin albumen, the mass ratio of calcium and magnesium silicate and fibroin albumen is 1~50:100.
2. novel calcium and magnesium silicate according to claim 1 and fibroin albumen complex stephanoporate bracket, which is characterized in that calcium
The partial size of magnesium silicate is 0.1~5 μm.
3. novel calcium and magnesium silicate according to claim 2 and fibroin albumen complex stephanoporate bracket, which is characterized in that calcium
Magnesium silicate is akermanite, become wollastonite, magnesium adulterates one or both of calcium silicates, merwinite and monticellite and
Two or more compounds.
4. novel calcium and magnesium silicate according to claim 3 and fibroin albumen complex stephanoporate bracket, which is characterized in that branch
Frame is porous structure, and porosity is 90%~96%.
5. novel calcium and magnesium silicate according to claim 2 and fibroin albumen complex stephanoporate bracket, which is characterized in that institute
State the compound that calcium and magnesium silicate is akermanite and diopside.
6. a kind of preparation of novel calcium and magnesium silicate Yu fibroin albumen complex stephanoporate bracket a method as claimed in any one of claims 1 to 5
Method, which is characterized in that steps are as follows:
1) calcium and magnesium silicate powder is added in n-butanol by the mass volume ratio of 0.25~20g:100mL, with 200rpm's
Speed is placed in mechanical ball mill 2h in ball grinder；
2) slurry of ball milling is then subjected to ultrasonic disperse, ultrasonic power 35W, frequency 40kHz；After ultrasonic 10min,
It is 8%~20% that the ratio of above-mentioned dispersion liquid 4:2 by volume, which is added dropwise to mass fraction, under the mixing speed of 200rpm
In silk fibroin protein solution, the mass ratio for controlling calcium and magnesium silicate and fibroin albumen is 1~50:100；
3) suspension mixed is placed in in -20~-5 °C of refrigerator freezing 10~for 24 hours, then defrosting 6h is obtained at room temperature
The silk fibroin bracket of white cleans bracket using deionized water, is freeze-dried bracket after cleaning n-butanol, obtains compound more
Hole bone tissue engineering scaffold.
7. the preparation method of novel calcium and magnesium silicate and fibroin albumen complex stephanoporate bracket according to claim 6,
It is characterized in that, using n-butanol crosslinking and freeze-drying, the bracket of preparation has the gap structure of three-dimensional communication, and porosity exists
90% or more, aperture is between 50~350 μm.
8. a kind of novel calcium and magnesium silicate a method as claimed in any one of claims 1 to 5 and fibroin albumen complex stephanoporate bracket are lacked in bone
Purposes in damage reparation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110877976A (en) * | 2019-11-26 | 2020-03-13 | 杭州电子科技大学 | Variable-cross-section high-strength degradable bar and manufacturing method thereof |
| CN110877977A (en) * | 2019-11-26 | 2020-03-13 | 杭州电子科技大学 | High-strength degradable bar and manufacturing method thereof |
| CN113499481A (en) * | 2021-06-18 | 2021-10-15 | 广东省科学院健康医学研究所 | Porous scaffold and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110877976A (en) * | 2019-11-26 | 2020-03-13 | 杭州电子科技大学 | Variable-cross-section high-strength degradable bar and manufacturing method thereof |
| CN110877977A (en) * | 2019-11-26 | 2020-03-13 | 杭州电子科技大学 | High-strength degradable bar and manufacturing method thereof |
| CN110877977B (en) * | 2019-11-26 | 2022-09-30 | 杭州电子科技大学 | High-strength degradable bar and manufacturing method thereof |
| CN113499481A (en) * | 2021-06-18 | 2021-10-15 | 广东省科学院健康医学研究所 | Porous scaffold and preparation method and application thereof |
| CN113499481B (en) * | 2021-06-18 | 2022-07-19 | 广东省科学院健康医学研究所 | Porous scaffold and preparation method and application thereof |
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